Cyclic catalytic upgrading of chemical species using metal oxide materials

ABSTRACT

Processes are disclosure which comprise alternately contacting an oxygen-carrying catalyst with a reducing substance, or a lower partial pressure of an oxidizing gas, and then with the oxidizing gas or a higher partial pressure of the oxidizing gas, whereby the catalyst is alternately reduced and then regenerated to an oxygenated state. In certain embodiments, the oxygen-carrying catalyst comprises at least one metal oxide-containing material containing a composition having one of the following formulas: (a) Ce x B y B′ z B″O δ , wherein B=Ba, Sr, Ca, or Zr; B′=Mn, Co, or Fe; B″=Cu; 0.01&lt;x&lt;0.99; 0&lt;y&lt;0.6; 0&lt;z&lt;0.5; and 1&lt;δ&lt;2.2; (b) Sr v La w B x B′ y B″ z O δ , wherein B=Co or Fe; B′=Al or Ga; B″=Cu; 0.01&lt;v&lt;1.4; 0.1&lt;w&lt;1.6; 0.1&lt;x&lt;1.9; 0.1&lt;y&lt;0.9; 0&lt;z&lt;2.2; and 3&lt;δ&lt;5.5).

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims the benefit under 35 U.S.C. § 119(e) of U.S.Provisional Patent Application No. 60/846,323 filed Sep. 21, 2006, thedisclosure of which is hereby incorporated herein by reference.

STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH OR DEVELOPMENT

The U.S. Government has a paid-up license in this invention and theright in limited circumstances to require the patent owner to licenseothers on reasonable terms as provided for by the terms of SmallBusiness Innovation Research (SBIR) Contracts No. DE-FG02-05ER84200 andDE-FG02-04ER83936 awarded by the U.S. Department of Energy, and ContractNo. NNC06CA53C awarded by NASA.

BACKGROUND

1. Field of Technology

This invention relates generally to the field of catalysis. Morespecifically, the invention relates to methods of using metal oxidematerials for catalytic upgrading of chemical species.

2. Description of Related Art

The general strategy of cyclic catalytic conversion and chemical loopinghas been reported previously in the literature. The chemical loopingpartial oxidation of hydrocarbons is taught by Zeng, et al.¹⁹⁻²¹ The useof iron oxides in coal gasification in a chemical looping system hasbeen previously reported for converting carbon monoxide in synthesis gasto Co₂ (for subsequent decarbonation).^(21,26) Additionally, its use ina thermal looping cycle in the same art was evident: thermal energydeposited into the oxygen carrier upon exposure to fuel could then bereleased upon air oxidation. A coal gasification system (by GE GlobalResearch) employing transition metal (including iron) oxides²⁷ has beenreported. Alstom Power has also reported a gasification system whichutilizes calcium oxide.²⁸

The use of metal oxide materials for chemical looping combustion ofnatural gas and methane has appeared in the literature frequently.¹⁻¹⁶The use of metal oxide materials for cyclic partial oxidation of gaseoushydrocarbons has appeared much less frequently in the literature.Nevertheless, in one instance NiO supported on Al₂O₃ was investigated inthe chemical looping reforming of methane.¹⁷ The process reported byLyon uses a packed bed reactor which is alternately exposed to naturalgas and air. The packing is a catalyst comprised of NiO, Fe₂O₃, MnO,CuO, CoO, CdO, ZnO or mixtures thereof. Lyon also reports a process forheat transfer by unmixed combustion. The process utilizes a reactorpacked with nickel oxide, copper oxide, cobalt oxide, silver oxide,tungsten oxide, manganese oxide, or molybdenum oxide which is exposed toa reducing gas, converting the metal oxides to the corresponding metals.The metals are converted back to the metal oxides upon exposure to anoxidizing gas. Additionally, strontium sulfate or barium sulfate can beemployed, which, when contacted with reducing gas, are converted to thecorresponding sulfides. In this manner, heat can be transferred to theendothermic process (reduction of oxidizing gas).

The chemical looping reforming of liquid fuels has not been reportedextensively. The only such prior art is due to Kunii and Kunugi whoreport a continuous process for catalytic gasification of heavyhydrocarbon oils,²² and that assigned to BOC who reported the use ofperovskitic metal oxides in the cyclic partial oxidation of liquid fuel.

The use of metal oxide materials in separating oxygen from air is anovel process for providing oxygen for various processes. However, itsuse has been reported in the literature. Specifically, the use ofperovskite metal oxides in the cyclic autothermal recovery (CAR) processutilizes the metal oxides as oxygen storage materials to provide oxygento a number of processes.¹⁸

There is continuing interest in oxygen-carrying materials for use in avariety of processes.

SUMMARY OF THE INVENTION

In accordance with certain embodiments of the present invention, aprocess is provided which comprises: alternately contacting anoxygen-carrying catalyst with a reducing substance, or a lower partialpressure of an oxidizing gas, and then with the oxidizing gas or ahigher partial pressure of the oxidizing gas, whereby the catalyst isalternately reduced and then regenerated to an oxygenated state. Theoxygen-carrying catalyst comprises at least one metal oxide-containingmaterial selected from the group consisting of: (a) compounds having theformula Ce_(x)B_(y)B′_(z)B″O_(δ), wherein B=Ba, Sr, Ca, or Zr; B′=Mn,Co, or Fe; B″=Cu; 0.01<x<0.99; 0<y<0.6; 0<z<0.5; and 1<δ<2.2; (b)compounds having the formula Sr_(v)La_(w)B_(x)B′_(y)B″_(z)O_(δ), whereinB=Co or Fe; B′=Al or Ga; B″=Cu; 0.01<v<1.4; 0.1<w<1.6; 0.1<x<1.9;0.1<y<0.9; 0<z<2.2; and 3<δ<5.5; (c) Ce_(1-x-y)Ni_(x)B_(y)O_(2-*),wherein B=Zr, Ba, Ca, La, or K; 0.02<x<0.1; 0<y<0.1; and 0.02<*<0.15;(d) M_(1-x-y)A_(x)(B)_(y)O_(z), wherein M=Co, Fe, or Mn; A=Ce, Zr, orboth; B=La or Ca; 0.01<x<0.99; 0.01<y<0.99; 2<z<3.5; and (x+y)≦1; (e)AB_(1-x)B′_(x)O_(y), wherein A=Sr or Ba, B=Ce or Zr, B′=Y or Yb, and0<x<0.5, on a support comprising MO_(x), wherein M=Ce, Mn, or Ni, or ona support comprising x % MO_(x)/y % A₂WO₄/(MgO or SiO₂), wherein M=Ce,Mn, or Ni, and A=Na or K, 1<x<3, and 3<y<8; (f) unary metal oxidesselected from the group consisting of Fe₂O₃, Fe₃O₄, MnO_(x), CoO_(x),NiO_(x), wherein 1<x<2, CaCo₃, Ca(OH)₂; (g) binary metal oxides selectedfrom the group consisting of FeTiO₃, Mn_(1-x)CuO₂, andMn_(1-x)Fe_(x)O_(y), wherein 0.01<x<0.99, 1<y<1.5; and (h) coal asheither as a catalyst material itself or as a support for the unary orbinary metal oxides. In some embodiments, the reducing substance, whencontacted with the oxygen-carrying catalyst, is converted to at leastone chemical product.

In certain embodiments, the reducing substance is one or more gas,liquid, or solid substance, or a mixture of any of those. In someembodiments, contacting the catalyst includes alternately exposing afixed bed containing the catalyst to the reducing substance and to theoxidizing gas, or exposing the fixed bed containing the catalyst to acontinuous feed of the oxidizing gas and intermittently feeding thereducing substance. In some embodiments, contacting the catalystincludes circulating the catalyst in a fluidized bed system during thealternate contacting of the oxygen-carrying catalyst with a reducingsubstance, or a lower partial pressure of an oxidizing gas, and thenwith the oxidizing gas or a higher partial pressure of the oxidizinggas.

In some embodiments, contacting the catalyst includes circulating thecatalyst in a fluidized bed system wherein the catalyst is reduced in areactor and is circulated to a regeneration unit for contacting with theoxidizing gas or higher partial pressure of the oxidizing gas.

In some embodiments, the reducing substance comprises a gaseoushydrocarbon, the chemical product is synthesis gas, and the catalyst isactive for catalyzing the partial oxidation of the hydrocarbon, whereinthe catalyst comprises (a) Ce_(x)B_(y)B′_(z)B′_(w)O_(δ), wherein B=Ba,Sr, Ca, or Zr; B′=Mn, Co, or Fe; B′=Cu; 0.01<x<0.99, 0<y<0.6, 0<w<0.5,and 1<δ<2.2, or (b) Ce_(1-x-y)Ni_(x)B_(y)O_(2-*), wherein B=Zr, Ba, Ca,La, or K; 0.02<x<0.1; 0<y<0.1; and 0.02<*<0.15, or (c)Sr_(v)La_(w)B_(x)B′_(y)B_(z)″O_(δ), wherein B=Co or Fe; B′=Al or Ga;B″=Cu, 0.01<v<1.4; 0.1<w<0.6; 0.1<x<1.9; 0.1<y<0.9; 0<z<2.2; and3<δ<5.5; or (d) M_(1-x-y)A_(x)(B)_(y)O_(z), wherein M=Co, Fe, or Mn;A=Ce, Zr, or both; B=La or Ca; 0.01<x<0.99; 0.01<y<0.99; 2<z<3.5; andx+y≦1. In some embodiments, the catalyst comprisesCe_(0.95)Ni_(0.05)O_(1.95), or Ce_(0.98)Ni_(0.02)O_(1.98), orCe_(0.90)Ni_(0.05)Ba_(0.05)O_(1.95).

In some embodiments, the reducing substance comprises a liquidhydrocarbon fuel, the product comprises synthesis gas, and the catalystis active for catalyzing the partial oxidation of the liquid hydrocarbonfuel, wherein the catalyst comprises Sr_(v)La_(w)B_(x)B′_(y)B″_(z)O_(δ),wherein B=Co or Fe, B′=Al or Ga, B″=Cu, 0.01<v<1.4, 0.1<w<1.6,0.1<x<1.9, 0.1<y<0.9, 0<z<2.2, and 3<δ<5.5. In some embodiments, theoxygen-carrying catalyst comprises Sr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O₅,or Sr_(0.31)La_(1.43)Co_(1.33)Al_(0.24)O_(4.81), orSr_(0.3)La_(1.27)Co_(1.74)Al_(0.21)O_(5.13), orSr_(0.02)La_(0.26)Fe_(1.63)Al_(0.02)Cu_(2.08)O_(4.97).

In certain embodiments, the reducing substance comprises liquidhydrocarbon fuel and lower partial pressure oxidizing gas incombination, the product comprises synthesis gas, the catalyst is activefor catalyzing the partial oxidation of the liquid hydrocarbon fuel, andthe process includes (a) co-feeding both the fuel and a lower partialpressure of an oxidizing gas to the catalyst in a reforming reactor, toreduce the catalyst, and produce synthesis gas, and (b) then exposingthe reduced catalyst to the higher partial pressure of the oxidizing gasin the absence of the fuel to regenerate the catalyst. In someembodiments, the process also includes separating H₂ from the synthesisgas. In some embodiments, the catalyst is contacted by the fuel andoxidizing gas at a temperature less than or equal to 900° C. In someembodiments, the catalyst comprises Sr_(v)La_(w)B_(x)B′_(y)B″_(z)O_(δ),wherein B=Co or Fe, B′=Al or Ga, B″=Cu, 0.01<v<1.4, 0.1<w<1.6,0.1<x<1.9, 0.1<y<0.9, 0<z<2.2, and 3<δ<5.5. In some embodiments, thecatalyst comprises (a) Sr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O₅, or (b)Sr_(0.31)La_(1.43)Co_(1.33)Al_(0.24)O_(4.81), or (c)Sr_(0.3)La_(1.27)Co_(1.74)Al_(0.21)O_(5.13), or (d)Sr_(0.02)La_(0.26)Fe_(1.63)Al_(0.02)Cu_(2.08)O_(4.97).

In certain embodiments, the reducing substance comprises a liquid fuelselected from the group consisting of diesel, gasoline, jet fuel,alcohols, glycerol, and plant oils. In certain embodiments, the reducingsubstance comprises coal particles, the product comprises synthesis gas,and the catalyst is active for catalyzing the gasification of the coalparticles, wherein the catalyst comprises at least one metaloxide-containing material selected from the group consisting of Fe₂O₃,Fe₃O₄, MnO_(x), CoO_(x), NiO_(x), FeTiO₃, CaCo₃, CaO, andMn_(1-x)Cu_(x)O_(y) or Mn_(1-x)Fe_(x)O_(y) wherein 0.01<x<0.99 and1<y<1.5, and coal ash either as a catalyst material itself or as asupport for the metal oxide-containing material. In certain embodiments,the reducing substance comprises biomass particles, the productcomprises synthesis gas, and the catalyst is active for catalyzing thegasification of the biomass particles, wherein the catalyst comprises atleast one metal oxide-containing material selected from the groupconsisting of Fe₂O₃, Fe₃O₄, MnO_(x), CoO_(x), NiO_(x), FeTiO₃, CaCo₃,CaO, and Mn_(1-x)Cu_(x)O_(y) or Mn_(1-x)Fe_(x)O_(y) wherein 0.01<x<0.99and 1<y<1.5, and coal ash either as a catalyst material itself or as asupport for the metal oxide-containing material.

In certain embodiments, the reducing substance comprises a hydrocarbon,the product comprises a dehydrogenated hydrocarbon, and the catalyst isactive for oxidatively dehydrogenating the hydrocarbon, wherein thecatalyst comprises: (a) Ce_(x)B_(y)B′_(z)B″_(w)O_(δ), wherein B=Ba, Sr,Ca, or Zr; B′=Mn, Co, or Fe; B″=Cu; 0.01<x<0.99, 0<y<0.6, 0<z>0.5,0<w<0.5, and 1<δ<2.2, or (b) Sr_(v)La_(w)B_(x)B′_(y)B″_(z)O_(δ), whereinB=Co or Fe, B′=Al or Ga, B″=Cu, 0.01<v<1.4, 0.1<w<1.6, 0.1<x<1.9,0.1<y<0.9, 0<z<2.2, and 3<δ<5.5, or (c) AB_(1-x)B′_(x)O_(y), whereinA=Sr or Ba, B=Ce or Zr, B′=Y or Yb, and 0<x<0.5, on a support comprisingMO_(x), wherein M=Ce, Mn, or Ni, or on a support comprising x % MO_(x)/y% A₂WO₄/(MgO or SiO₂), wherein M=Ce, Mn, or Ni, and A=Na or K, 1<x<3,and 3<y<8. In some embodiments, the catalyst comprisesSr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O₅, orSr_(0.31)La_(1.43)Co_(1.33)Al_(0.24)O_(4.81), orSr_(0.3)La_(1.27)Co_(1.74)Al_(0.21)O_(5.13).

In certain embodiments, the reducing substance comprises a hydrocarbon,the product comprises an oxidatively functionalized hydrocarbon, and thecatalyst is active for catalyzing the selective oxidation of thehydrocarbon by which at least one oxygenous function is inserted intothe hydrocarbon, wherein the catalyst comprises: (a)Ce_(x)B_(y)B′_(z)B″_(w)O_(δ), wherein B=Ba, Sr, Ca, or Zr; B′=Mn, Co, orFe; B″=Cu; and 0.01<x<0.99, 0<y<0.6, 0<w<0.5, and 1<δ<2.2), or (b)Sr_(v)La_(w)B_(x)B′_(y)B″_(z)O₆, wherein B=Co or Fe, B′=Al or Ga, B″=Cu,0.01<v<1.4, 0.1<w<1.6, 0.1<x<1.9, 0.1<y<0.9, 0<z<2.2, and 3<δ<5.5). Insome embodiments, the catalyst comprisesSr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O₅, orSr_(0.31)La_(1.43)Co_(1.33)Al_(0.24)O_(4.81) orSr_(0.3)La_(1.27)Co_(1.74)Al_(0.21)O_(5.13).

Also provided in accordance with certain embodiments of the presentinvention is a process for separating oxygen from air, comprising: (1)cyclically adsorbing and desorbing oxygen on an oxygen-carrying catalystcomprising (a) Ce_(x)B_(y)B′_(z)B″_(w)O_(δ), wherein B=Ba, Sr, Ca, orZr; B′=Mn, Co, or Fe; B′=Cu; and 0.01<x<0.99, 0<y<0.6, 0<w<0.5, and1<δ<2.2), or (b) Sr_(v)La_(w)B_(x)B′_(y)B″_(z)O_(δ) (where B=Co or Fe,B′=Al or Ga, B′=Cu, 0.01<v<1.4, 0.1<w<1.6, 0.1<x<1.9, 0.1<y<0.9,0<z<2.2, and 3<δ<5.5, or (c) Sr_(w)La_(x)Al_(y)(B)_(z)O_(2-α), whereinB=Co, Fe, Cu or a combination of any of those, 0.01<w<1, 0.01<x<1,0.01<y<1, 0.01<z<1, and 0<α<1.

In some embodiments, of an above-described oxygen separation process,adsorbing comprises exposing the catalyst to pressurized air, and thedesorbing comprises exposing the catalyst to a vacuum when the catalystcontains adsorbed oxygen. In some embodiments, the catalyst comprisesSr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O₅, orSr_(0.3)La_(1.27)Co_(1.74)Al_(0.21)O_(5.13), orSr_(0.31)La_(1.43)Co_(1.33)Al_(0.24)O_(4.81), orSr_(0.02)La_(0.26)Fe_(1.63)Al_(0.02)Cu_(2.08)O_(4.97), orCe_(0.5)Fe_(0.1)Cu_(0.4)O₂, or CeCo_(0.5)Cu_(0.5)O₃, orCe_(0.12)Mn_(0.34)Co_(0.54)O_(1.64), orCe_(0.45)Zr_(0.05)Mn_(0.45)Cu_(0.05)O_(1.7). In some embodiments thecatalyst is supported on a sintered metal fiber filter.

In accordance with certain embodiments of the invention, the reducingsubstance in an above-described process comprises a combustible wastematerial, the product is char and volatiles, and the catalyst comprisesa metal oxide that is active for pyrolyzing the waste material.

Also provided in accordance with certain embodiments is a process forthe cyclic catalytic partial oxidation of a carbon-containing feedstockwhich comprises (a) in an oxidation stage, passing air over a catalystcomprising a metal or metal oxide that is capable of capturing oxygenfrom the air, to produce an oxidized catalyst and producing an effluentcomprising oxygen-reduced air; (b) passing the feedstock over theoxidized catalyst in a reduction stage to create a product gascomprising carbon monoxide and hydrogen, wherein the oxidized catalystbecomes reduced or partially reduced creating a metal or metal oxide;and (c) repeating (a) to reoxidize the catalyst. In some embodiments,the catalyst comprises at least one metal oxide selected from the groupconsisting of: (i) Ce_(x)B_(y)B′_(z)B″O_(δ), wherein B=Ba, Sr, Ca, orZr; B′=Mn, Co, or Fe; B″=Cu; 0.01<x<0.99; 0<y<0.6; 0<z<0.5; 1<δ<2.2;(ii) Ce_(1-x-y)Ni_(x)B_(y)O_(2-*), wherein B=Zr, Ba, Ca, La, or K;0.02<x<0.1; 0.01<y<0.1; and 0.02<*<0.15, and (iii)Sr_(v)La_(w)B_(x)B′_(y)B″_(z)O_(δ), wherein B=Co or Fe; B′=Al or Ga;B″=Cu; 0.01<v<1.4; 0.1<w<1.6; 0.1<x<1.9; 0.1<y<0.9; 0<z<2.2; and3<δ<5.5. In some embodiments the feedstock comprises glycerol.

Certain other embodiments of the present invention provide a process forthe direct generation of hydrogen peroxide which comprises: (a) in anoxidation stage, passing air over a catalyst comprising a metal or metaloxide that is capable of capturing oxygen from the air, to produce anoxidized catalyst and producing an effluent comprising oxygen-depletedair; (b) passing hydrogen over the oxidized catalyst in a reductionstage to create a product gas comprising hydrogen peroxide, wherein theoxidized catalyst becomes reduced or partially reduced; and (c)repeating (a) to reoxidize the catalyst, wherein the catalyst comprisesa nanostructured catalyst comprising a carbon- or nitrogen-containingmetal complex deposited in the pores of a mesoporous support material,wherein the metal is selected from the group consisting of Pt, Pd, Au,Ag, Co, Ni, Cu or Ru.

In accordance with still another embodiment of the invention a processfor cyclic reduction of carbon dioxide is provided which comprises: (a)in an oxidation stage, passing carbon dioxide over a catalyst comprisinga metal or metal oxide that is capable of capturing oxygen from thecarbon dioxide, to produce an oxidized catalyst and producing aneffluent comprising carbon monoxide; (b) in a reduction stage, passinghydrogen over the oxidized catalyst to produce water, whereby theoxidized catalyst becomes reduced or partially reduced; and (c)repeating (a) to reoxidize the catalyst, wherein the catalyst comprisesiron. In some embodiments, water and carbon monoxide products arerecovered.

BRIEF DESCRIPTION OF THE DRAWINGS

For a detailed description of the preferred embodiments of theinvention, reference will now be made to the accompanying drawings inwhich:

FIG. 1A is a schematic diagram of a process in which an oxygen-carryingmaterial is alternately reduced and then oxidized, in accordance withcertain embodiments of the invention.

FIG. 1B is a schematic diagram of a process in which an oxygen-carryingmaterial alternately adsorbs and desorbs oxygen when subjected to cyclicapplications of pressurized air, with heating-cooling, and thensubjected to vacuum and increased temperature to release O₂, inaccordance with certain embodiments of the invention.

FIG. 1C is a schematic diagram of a process in which an oxygen-carryingmaterial is alternately reduced and then oxidized by exposure to anoxidizing gas at higher partial pressure followed by exposure of thematerial to the oxidizing gas at a lower partial pressure together witha hydrocarbon feed, in accordance with an embodiment of the invention.

FIG. 2 illustrates methane conversion of selected catalysts over timeafter initial product formation, in accordance with certain embodimentsof the invention.

FIG. 3 illustrates selectivity towards POM over time after initialproduct formation of selected catalysts, in accordance with certainembodiments of the invention.

FIG. 4 illustrates plots of product levels generated versus time in thechemical looping gasification of Wyodak coal over 6.9 g (10 ml) 100-170mesh catalyst, in accordance with certain embodiments of the invention.

FIG. 5 illustrates lower heating values for undiluted product gasesobtained from gasification experiments using certain catalystembodiments of the invention.

FIG. 6 illustrates a plot of electrochemical sensor response versusadsorbent temperature using certain catalyst embodiments of theinvention.

FIG. 7 illustrates a schematic flow diagram of a fluidized bed systemfor chemical looping using certain catalysts, in accordance withembodiments of the invention.

FIG. 8 illustrates a schematic of a fixed bed reactor unit used for apartial oxidation chemical looping process, in accordance with certainembodiments of the invention.

FIG. 9 illustrates a schematic of a fixed bed chemical looping systememploying multiple fixed bed reactors in sequence, which is used inaccordance with certain embodiments of the invention.

FIG. 10 is a schematic illustration of the preparation procedure formetal oxide coated sintered metal fiber based partial oxidationcatalysts for use in accordance with certain embodiments of theinvention.

FIG. 11 is a schematic illustration of a fluidized bed based chemicallooping process for cyclic reduction of Co₂ and subsequent reduction ofiron oxide to metallic iron, in accordance with certain embodiments ofthe invention.

FIG. 12 illustrates a fixed bed cyclic (chemical looping) systemutilizing a metal oxide oxygen carrying material supported on sinteredmetal fiber filters (SMFFs) for the separation of oxygen from air, inaccordance with certain embodiments of the invention.

FIG. 13 illustrates a schematic diagram of overall cyclic partialoxidation reformer (CycloFormer™) system, in accordance with certainembodiments of the invention.

FIG. 14 illustrates a conception of a CycloFormer™ in accordance with anembodiment of the invention

FIG. 15 is a schematic illustration of a process concept which employsan oxygen carrier for oxygen separation and coal gasification, inaccordance with certain embodiments of the invention.

FIG. 16 is a schematic illustration of an oxidative dehydrogenationprocess employing an oxygen carrying catalyst for oxygen separation andfluidization, in accordance with certain embodiments of the invention.

FIG. 17 is a plot of product evolution versus time between theappearance of products and sampling time for 99% Glycerol over aSr_(1.4)La_(0.6)Cu_(1.6)Al_(0.4)O_(5.3) catalyst at 700° C., inaccordance with certain embodiments of the invention.

FIG. 18 is a plot of the effect of water and KOH addition (to simulatecrude glycerol) on hydrogen production at 800° C. by an oxygen-carryingcatalyst, in accordance with certain embodiments of the invention.

FIG. 19 is a plot demonstrating the stability of theSr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O_(5.3) coated YSZ granules forreforming glycerol/water/KOH mixture (simulated crude glycerol) in aprocess according to an embodiment of the invention.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The metal oxide materials Ce_(x)B_(y)B′_(z)B″_(w)O_(δ) (where B=Ba, Sr,Ca, or Zr; B′=Mn, Co, or Fe; B″=Cu; and 0.01<x<0.99, 0<y<0.6, and0<w<0.5); Sr_(v)La_(w)B_(x)B′_(y)B″_(z)O_(δ) (where B=Co or Fe, B′=Al orGa, B″=Cu, 0.01<v<1.4, 0.1<w<1.6, 0.1<x<1.9, 0.1<y<0.9, 0<z<2.2, and3<δ<5.5); unary metal oxides Fe₂O₃, Fe₃O₄, MnO_(x), CoO_(x), andNiO_(x); binary metal oxides FeTiO₃, Mn_(1-x)Cu_(x)O_(y), andMn_(1-x)Fe_(x)O_(y); and coal ash either as a catalyst material itselfor as a support for the above unary or binary metal oxides are employedin a process (FIG. 1) in which an oxygen storing or oxygen carryingcatalyst comprised of one of the materials is exposed to a gaseous,liquid or solid chemical substance, effecting oxidation of the substanceand reduction of the catalyst material. The catalyst material in thereduced state is then exposed to an oxidizing gas (e.g., air), causingthe catalyst to be regenerated into its oxidized state and removingcarbonaceous or other material that may have accumulated during exposureto the reducing substance. Recently some of the materials(Sr_(v)La_(w)B_(x)B′_(y)B″_(z)O_(δ)) have been shown to be active inFischer-Tropsch synthesis of hydrocarbons from CO and hydrogen. A commonfeature of these materials that has been recently identified is theirconsiderable oxygen storage capacity (OSC). This is the weight fractionof oxygen that can be incorporated into the materials and thensubsequently removed. The ability of the materials to be reversibly andreproducibly subjected to such oxidation-reduction cycles enables themto be employed both as catalysts and as oxygen carriers and catalystsfor various oxidation chemistries. This makes possible their use in avariety of applications, which are exemplified herein.

Such applications include, but are not limited to, the following: (1)Partial oxidation of liquid fuels. Organic liquids, including jet fuel,diesel, alcohols, and plant-seed oils can be processed to providesynthesis gas (CO+H₂) for various applications including combustion andfuel cells. In a conventional mode, the catalyst is incorporated intopellets or onto a monolith and a mixture of air and atomized orvaporized fuel introduced over the catalyst. In the cyclic (chemicallooping or pulsed feed) mode, fine droplets or vapor of the fuel and airis introduced over the catalyst bed along with a carrier gas. The feedto the bed is switched between this mixture and air (or other oxidant),as illustrated in FIG. 1A. Alternatively, air can be fed continuously tothe bed and the liquid feed delivered to the reactor (as droplets orvapor) intermittently (as pulsed feed), as illustrated in FIG. 1C.Finally, the liquid feed may be continuously or semi-continuously fedinto a reactor containing the catalyst, which continuously circulatesbetween this reactor and a regenerator in which the oxygen carrier isre-oxidized and carbonaceous films and impurities are burned off. Thisis similar to a fluid catalytic cracking (FCC) reactor. (2) Partialoxidation of gaseous fuels (FIG. 1A). In this case, the feed to thereactor is switched between air and a gaseous fuel (natural gas,methane, or other hydrocarbons. Alternatively, as in (1), the fuel maybe fed to a reactor in which catalyst is continuously circulated betweena fuel partial oxidation reactor and a regenerator. (3) Gasification ofsolid fuels. Coal, biomass, industrial waste (petroleum reside,plastics, tire rubber, etc.) is continuously or semi-continuously fed toa reactor containing a fluidized or moving bed of the oxygen carryingcatalyst (FIG. 1A). The catalyst circulates between the coalgasification bed and a regeneration bed where the catalyst is exposed toair and reoxidized. Adsorbed impurities liberated from coal can also bereleased and removed from the regenerator exhaust by scrubbing or othercapture processes. (4) Oxygen separation from air. As illustrated inFIG. 1B, a reduced carrier is exposed alternately to air at sometemperature and pressure and then to vacuum, lower pressure, a highertemperature, or a combination or lower pressure and higher temperaturewhich causes adsorption equilibrium to shift towards the gas phase. (5)Oxidative dehydrogenation of hydrocarbons. A hydrocarbon (e.g., alkaneor olefin) is passed over an oxygen carrying catalyst which is activefor the oxidative dehydrogenation of the hydrocarbon. The process may becarried out in either circulating fluidized bed or fixed bed, in pulsedco-feed modes. (6) Selective oxidation of hydrocarbons and otherorganics. This consists of the functionalization of hydrocarbons by thecatalytic insertion of oxygenous functions on carbon atoms or in theoxidation of other groups, e.g., of alcohols to aldehydes. Circulatingfluid beds and fixed beds utilizing pulsed co-feed are applicablereactor types, similar to FIGS. 1A and 1C. (7) Cyclic catalyticoxidation/reduction process for gasification of waste, e.g., waste feed,char, volatiles.

Oxygen carrying catalysts utilized in the processes described herein arepreferably prepared by co-precipitation, urea precipitation, or sol-gelsynthesis, using known techniques. The metal oxide catalysts may takethe form of granules, pellets, or monolithic structures. Coal ash mayalso be used as a support for selected unary (Fe₂O₃, Fe₃O₄, MnO_(x),CoO_(x), and NiO_(x)) and binary (FeTiO₃, Mn_(1-x)Cu_(x)O_(y), andMn_(1-x)Fe_(x)O_(y)) metal oxides. The metal oxide materials and coalash may be bound with an inorganic binder such as silica, titania,magnesia, boehmite, or zirconia. As indicated above, fixed beds of thesecatalysts may be either exposed to alternating air and feed or to acontinuous feed of air and intermittent (pulsed) feed of feedstock. Invarious embodiments, fluidized bed systems comprise one, two, or evenmore fluidized beds, as desired for a particular application.Alternating exposure to air and feed is achieved either by means of aset of valves (for a single bed) or in the case of two or more beds bycirculation of the oxygen carrier between the reactor and regeneratorbeds.

Embodiments of the compositions and methods disclosed herein (1) makepossible the production of unique products (2) offer new modes ofoperation, and (3) employ new oxygen carrying materials. Certainembodiments employ selected oxygen-carrying materials for the selectiveconversion of hydrocarbons and other fuels to synthesis gas and othermore valuable species. Some of the specific materials identified forliquid fuels reforming have not been previously employed. Likewise, useof the metal oxide materials Sr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O₅,Sr_(0.3)La_(1.27)Co_(1.74)Al_(0.21)O_(5.13),Sr_(0.31)La_(1.43)Co_(1.33)Al_(0.24)O_(4.81), andSr_(0.02)La_(0.26)Fe_(1.63)Al_(0.02)Cu_(2.08)O_(4.97) as well as ofCe_(0.5)Fe_(0.1)Cu_(0.4)O₂, CeCo_(0.5)Cu_(0.5)O₃,Ce_(0.12)Mn_(0.34)Co_(0.54)O_(1.64), andCe_(0.45)Zr_(0.05)Mn_(0.45)Cu_(0.05)O_(1.7) for air separation has notbeen previously described.

Several applications described herein are distinctive in the mode ofoperation employed. For example, (1) coal gasification by an indicatedmethod utilizes direct contact of coal with an air oxidized metal oxidematerial, producing synthesis gas; (2) natural gas chemical loopingpartial oxidation uses a fixed bed of oxygen-carrying catalyst which isalternately exposed to air and natural gas; (3) chemical looping liquidfuels reforming utilizes a fixed catalyst bed with continuous air feedand intermittent, pulsed delivery of liquid fuel. Representativeexamples are provided below to further elucidate the preferredembodiments.

Example 1 Cyclic Catalytic (Chemical Looping) Partial Oxidation ofMethane

The catalysts used in these examples were prepared by coprecipitation. Afixed bed of fine catalyst granules (0.5 g) was employed. The catalystwas heated to 750° C. and was exposed to air to oxidize the catalyst.The reactor was then purged with helium and pure methane introduced.Space velocity was 6000 ml/g·min. Measurement of H₂, CO, Co₂, and CH₄was performed by injection of product stream samples into a gaschromatograph. Samples were taken at some time after the initialobservation of products. The catalyst was then reoxidized before anotherproduct stream sample was taken at a different time interval afterappearance of products. Data for a number of catalysts are summarized inFIGS. 2 and 3 (in both of the figures the shown reactor operates at 750°C., catalyst mass is 0.5 g, and methane flow rate is 50 ml/min) whichshow methane conversion and selectivity to partial oxidation productsversus the time elapsed after introduction of methane, respectively.

Example 2 Chemical Looping Coal Gasification

A bed of granular catalyst material of mesh size 40-100 mesh heated tobetween 650° C. and 850° C. was fluidized using atmospheric pressureair, being exposed to air for 5-20 minutes. Fluidization with air wasinterrupted and steam introduced into the gasifier. Wyodak coal of meshsize 20-40 was then introduced at a rate of 0.33 g/min for 1.75-2.75minutes. The coal feed was interrupted and allowed to contact thefluidized catalyst for 10-20 minutes. Products were sampled with a gastight syringe and analyzed using gas chromatography. The resultingproduct analysis versus contact time between coal and catalyst for anFe₃O₄ catalyst is shown in FIG. 4, where the catalyst is fluidized withsteam at a feed rate of 4.6 L/min) at: A) 795° C. Coal feed rate=0.33g/min. Coal feed interval=first 2.75 min of run. B) 825° C. Coal feedrate=3.3 g/min. Coal feed interval=first 1.75 min of run.

The lower heating value of the gas product versus temperature obtainedusing several different catalysts in such experiments (absent steam andusing nitrogen gas for fluidization) is plotted in FIG. 5 (the heatcontent of coal (as received)=8593 Btu/lbm).

Example 3 Cyclic Catalytic Partial Oxidation of Liquid Fuels

A bed of grains of catalyst material was oxidized in air at atemperature between 600° C. and 750° C. for 5-20 minutes. Liquid fuelwas then introduced into the reactor at a flow rate of 0.05 ml/min. Thegas flow emerging from the reactor was measured using a bubble flowmeter. Gaseous products (CO, Co₂, H₂, and CH₄) were analyzed using gaschromatography. Experimental conditions employed and data obtained overpreferred catalyst materialsSr_(0.31)La_(1.43)Co_(1.33)Al_(0.24)O_(4.81) (1) andSr_(0.3)La_(1.27)Co_(1.74)Al_(0.21)O_(5.13) (2) is presented in Tables 1and 2.

TABLE 1 Summary of Experimental Conditions Employed with PreferredCatalyst Materials Bed Inlet Catalyst Volume Feed Flow Cat. Exp. Wt (g)(cm³) Gas (ml/min) GHSV (h⁻¹) LHSV (h⁻¹) T (° C.) 1 PI-1 0.5 0.459 He 262388 6.5 700 PI-2 0.448 0.486 Air 125 10845 6.2 600 PI-3 0.5 0.459 Air159 14607 6.5 700, 800 2 PI-4 0.5 0.338 He 26 3244 8.9 700 PI-5 0.50.493 Air 159 13600 6.1 800

TABLE 2 Summary of Product Data for Preferred Catalysts % % % % POXCracking CH₄ DOX H₂ CO CH₄ CO₂ Tot. Prod. Cat. Exp. H₂ CO CH₄ CO₂ H₂/COSelect. Select. Select. Select. mL/min mL/min mL/min mL/min mL/min 1PI-1 37.7 16.4 2.2 7.9 2.4 31.4 49.1 4.2 15.2 34.1 15.0 1.9 7.4 58.4PI-2 22.8 10.8 1.0 12.3 2.2 28.3 36.9 2.7 32.2 44.0 21.1 2.0 23.4 90.6PI-3 13.0 12.5 2.8 11.4 1.0 38.4 18.3 8.4 34.9 25.0 23.8 5.2 21.3 75.3 2PI-4 60.4 9.1 5.0 0.6 7.0 12.0 80.7 6.5 0.8 80.7 12.1 6.6 0.8 100.1 PI-526.7 25.1 0.9 2.3 1.1 79.7 10.4 2.7 7.2 64.1 60.3 2.1 5.5 132.0

Example 4 Separation of Oxygen from Air by Adsorption-Desorption Cycles

A bed (0.25-0.45 g) of adsorbent material in granular (40-100 mesh) formwas heated (at 10° C./min) from 100° C. to 700° C. in air (gas hourlyspace velocity=6000 h⁻¹) and held at 700° C. for 1 hour. The temperaturewas then decreased from 700° C. to 100° C. at 10° C./min under air andwas held at 100° C. for 30 minutes before changing the purge gas tohelium. The reactor was then purged for 30 minutes at a temperature of100° C. The adsorbent bed temperature was then increased at 10° C./minunder helium and the effluent from the reactor monitored with anelectrochemical oxygen sensor. The sensor output was recorded, givingrise to graphs of the type shown in FIG. 6. Data obtained over keymaterials is presented in Table 3.

TABLE 3 Summary of Oxygen Desorption Data for Materials of the InventionCat. GHSV, Cycle Total Peak Exp # Cat. Comp. Mass, g hr⁻¹ # Area 1 Fe₃O₄0.2602 6000 1 112,590 1 Fe₃O₄ 0.2602 6000 2 94,071 1 Fe₃O₄ 0.2602 6000 378,209 2 Sr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O₃ 0.2582 4000 1 537,652 2Sr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O₃ 0.2582 4000 2 430,257 3Ce_(0.5)Fe_(0.5)O_(n) 0.3703 6000 1 16,673 4Sr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O₃ 0.2488 6000 1 297,670 4Sr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O₃ 0.2488 6000 2 245,425 5Ce_(0.5)Fe_(0.1)Cu_(0.4)O₂ 0.2939 6000 1 265,759 5Ce_(0.5)Fe_(0.1)Cu_(0.4)O₂ 0.2939 6000 2 185,749 6 CeCo_(0.5)Cu_(0.5)O₃0.3469 6000 1 305,829 6 CeCo_(0.5)Cu_(0.5)O₃ 0.3469 6000 2 218,455 7Ce_(0.12)Mn_(0.34)Co_(0.54)O_(1.64) 0.2552 6000 1 744,629 7Ce_(0.12)Mn_(0.34)Co_(0.54)O_(1.64) 0.2552 6000 2 592,802 7Ce_(0.12)Mn_(0.34)Co_(0.54)O_(1.64) 0.2552 6000 3 586,605 10Sr_(0.02)La_(0.26)Fe_(1.63)Al_(0.02)Cu_(2.08)O_(4.97) 0.2498 6000 1672,585 10 Sr_(0.02)La_(0.26)Fe_(1.63)Al_(0.02)Cu_(2.08)O_(4.97) 0.24986000 2 667,273 11 Ce_(0.45)Zr_(0.05)Mn_(0.45)Cu_(0.05)O_(1.7) 0.22076000 1 991,508

Example 5 Auto-Thermal Reforming Catalysts for Use in Chemical LoopingSystems

A fluidized bed cyclic redox (chemical looping) system utilizing a metaloxide oxygen carrier for partial oxidation of methane for the productionof syngas/hydrogen is shown in FIG. 7. The reformer consists of a highvelocity air fluidized riser connected, through loop seals, to a lowvelocity methane fluidized riser. Carbon deposition and steamrequirements and, possibly, the need for a prereformer are reduced oreliminated by this cyclic mode. This cyclic operation also eliminatesthe need for an expensive air separation unit or for H₂/N₂ separation.

Compositions possessing the general formulaCe_(1-x-y)Ni_(x)B_(y)O_(2-*), where B=Zr, Ba, Ca, La, or K; 0.02<x<0.1;and 0.02<y<0.1 which can stand alone or can be deposited on a highsurface area support such as alumina, magnesium oxide, ceria, magnesiumaluminate, aluminosilicates, or mesoporous silica materials.

Unsupported metal oxide catalysts are prepared by: (i) co-precipitation,(ii) urea precipitation, and (iii) sol gel synthesis, using knowntechniques. Initially, a number of the compositional parameters x, y,and z are utilized, but following coarse screening, these stoichiometricsubscripts are varied based on the experimental results according tomixture and/or Simplex designs.

Supported metal oxide catalysts are prepared through wetnessimpregnation utilizing compositions of preferred unsupported catalystson various supports. Synthesis includes suspending 10 grams of support(Al₂O₃, MgO, CeO₂, or MgAl₂O₄) in an aqueous solution of the desiredmetals (Ce) nitrate and (Ni) nitrate without any supernatant liquid. Theslurry is dried by evaporation and then heated in an oven at 120° C. for8 hours. Following drying, the solid is calcined at 600° C. for 12-24hours in order to decompose the nitrate and provide a supported metaloxide product.

It has been shown (see Example 1 and FIGS. 2 and 3) that selectedcatalysts have potential for the chemical looping partial oxidation ofmethane with CH₄ conversion, syngas selectivity and productivitycomparable or superior to that of methane steam reforming, but at lowertemperature (750° C.) and in an exothermic regime of operation.

Example 6 Fixed Bed Chemical Looping Partial Oxidation Catalysts on SMFFSupports

A metal oxide oxygen carrying catalyst supported on a sintered metalfiber filter (SMFF) is utilized in a fixed bed cyclic redox (chemicallooping) system for partial oxidation of methane for the production ofsyngas/hydrogen. The reformer consists of one or more heated beds ofSMFF supported, sulfur tolerant partial oxidation catalyst and operatesby alternate exposure to air and gas. Carbon deposition and steamrequirements and, possibly, the need for a prereformer are reduced oreliminated by this cyclic mode. This cyclic operation also eliminatesthe need for an expensive air separation unit or for H₂/N₂ separation.

Sintered metal fiber filters (SMFF), consisting of thin metal filaments(d=2-30 μm), were used as the catalyst supports and offer manyadvantages over ceramic and unsupported material, including: (a) SMFFsare more mechanically and chemically stable than random beds and ceramicmonoliths; (b) SMFF's possess a uniform highly porous (70-90% porosity)3D macrostructure which helps provide a low pressure drop during gaspassage; (c) metal fibers have a high thermal conductivity, especiallywhen compared to ceramics, which provides a radial heat transfercoefficient within the reactor bed the result of which is nearlyisothermal conditions within the beds; (d) channeling is also avoidedbecause the micro-fiber matrix acts as a micron scale static mixer; (e)thin coatings, for helping to increase surface area and reduceagglomeration of the impregnated material, are also possible because ofthe small fiber diameter; (f) the small diameters minimize thecoefficient of thermal expansion of the metal fiber thereby eliminatingcracking of the oxide layer; and (g) the thin oxide layers also lead toimproved mass transfer resistance since the pores of the oxide layer areshort and the reactant diffusion does not limit the reaction.

Materials were designed for use in one or more switched feed fixed beds(see FIGS. 8 and 9). Unsupported metal oxide catalysts were prepared byeither: (i) co-precipitation, (ii) urea precipitation, and (iii) sol gelsynthesis. Initially, a number of the compositional parameters x, y, andz are utilized, but following coarse screening, these stoichiometricsubscripts are varied based on the experimental results according tomixture and/or Simplex designs discussed below.

Sintered metal fiber filters (FECRALLOY™ supplied by Bekaert FiberTechnology, Belgium) are coated with CeO₂ and/or a variety of ceriumbased mixed metal oxides. These coated fibers are then impregnated withmixed metal oxide materials having the general formulaCe_(1-x-y)Ni_(y)(A)_(z)O_(2-δ) (where A is a basic metal dopant such asLa, Ba, Ca, or Sr). See FIG. 10, (sol-gel synthesis of metal oxidecoated sintered metal fibers (A to B) is followed by impregnation ofcoated surface with mixed metal oxide catalysts (B to C)).

Preparation of the cerium oxide SMFF coatings is achieved through thesol-gel solvent evaporation method. This consists of adding theappropriate metal salts or alkoxides (i.e., acetylacetonates,isopropoxides) to a chosen solvent (various alcohols). A stabilizer,such as acetylacetonate, is added in an attempt to keep the sol solutionclear and particle free to prevent large particles from clogging thefilter during dip-coating and spraying. The stabilizer addition isfollowed by addition of a calculated amount of water and acid (HCl,HNO₃) or base for hydrolysis and condensation to form precipitate free,homogeneous, non-water sensitive, stable sols. The gels are aged for achosen time and sprayed onto the sintered metal fiber filter or thefilter is immersed in the gel and removed. Regardless of applicationmethod the filter is then left to dry for 12-24 hours and then calcinedin air at 400° C.-700° C.

Impregnation of the coated SMFFs is done through wet impregnation orincipient wetness impregnation. In wet impregnation the chosen metalsalt(s) is(are) combined in previously determined ratios and dissolvedin methanol or water. Coated sintered metal fibers are then immersed inthe solution for a chosen time frame, extracted, allowed to either agein air and then dried in a 100° C. oven overnight or dried immediately.Dried fiber filters are then calcined in air for 4-8 hours at 700°C.-1000° C. In incipient wetness impregnation chosen metal salt(s)is(are) once again combined, but dissolved in a volume of methanol orwater equal or slightly less than the pore volume of the support. Thismixture is then carefully applied to the surface of the coated metalfiber by dropwise addition or by fine spray. Impregnated metal fiberfilters are either allowed to age for a given time and then dried in a100° C. oven overnight or dried immediately. Dried fiber filters willthen be calcined in air for 4-8 hours at 700° C.-1000° C.

Example 7 Reduction of Co₂

A fluidized bed cyclic redox (chemical looping) system utilizing an ironoxide carrier for cyclic reduction of carbon dioxide to carbon monoxide(equations 1,2) and the subsequent reduction of iron oxide to metalliciron (equations 3,4) is described.

Fe+Co₂

FeO+CO ΔH=10.98 kJ mol⁻  (1)

3FeO+Co₂

Fe₃O₄+CO ΔH=−19.42 kJ mol⁻¹  (2)

Fe₃O₄+H₂

3FeO+H₂O ΔH=60.6 kJ mol⁻¹  (3)

FeO+H₂

Fe+H₂O ΔH=30.2 kJ mol⁻¹  (4)

This process embraces in a new way two well-known and proven processes,the reduction of iron oxide with hydrogen and the oxidation of iron withCo₂, by linking them together within a chemical looping system. Thisenables production of CO and H₂O, both of which can be used for makingfuels, other commodity chemicals, and/or used for life support purposes.While it would be possible to generate both CO and H₂O using a reversewater-gas-shift (RWGS) reactor, embodiments of the present system andprocess allow easier separation of products, provide a system capable ofperforming other redox processes, and also provide a low temperature wayof recovering metallic iron from iron oxide ores (FIG. 11).

Iron oxides may be synthesized by two different types of precipitationreactions. The first consists of adding a solution of precipitatingagent (NaOH, KOH, Na₂Co₃, K₂Co₃, NH OH, (NH₄)₂Co₃, sodium or potassiumoxalate) dropwise into a aqueous or methanol solution of the metal ions,resulting in precipitation of the insoluble metal hydroxides orcarbonates. The second type, urea gelation/precipitation, consists ofadding a large excess of urea to an aqueous solution of the metal ions.By boiling the resulting solution at 100° C. for eight hours, addingwater as necessary, a slow decomposition of the urea ensues, creating abasic solution over time which in turn results in the slow precipitationof the desired products. The precipitate of either method are thencollected through vacuum filtration, dried in an oven at 100° C. for 24hours, ground into a fine powder using an alumina mortar and pestle, andthen calcined, in air or in a reducing environment depending on thedesired product, at temperatures between 600° C. and 900° C. for 4-12hours. This process is applicable for reducing Co₂ concentrations ingases, and utilizing the water and carbon monoxide products. Forexample, they may be used in fuels, as feedstocks for making commoditychemicals, and/or used for life support purposes. One particularapplication is for reducing the Co₂ atmosphere on Mars, which isprimarily composed of Co₂.

Example 8 Supported Oxygen-Carrying Materials for Oxygen Separation andSupply

An exemplary fixed bed cyclic (chemical looping) system utilizing ametal oxide oxygen carrying material supported on sintered metal fiberfilters (SMFFs) for the separation of oxygen from air is described inthis example and schematically illustrated in FIG. 1B. The separationunit consists of one or more heated beds of SMFF supported metal oxideand would operate by alternate exposure to pressurized air and vacuumwhile undergoing temperature ramps from 200° C.-400° C. Embodiments ofthis system would compete directly with more costly cryogenic separationplants as well as pressure swing adsorption systems which currentlyproduce a lower purity of oxygen. Embodiments of this technology produceinexpensive, high purity oxygen streams for use in processes such ascoal gasification, integrated gasification combined cycle (IGCC), andoxycombustion leading to an exhaust stream void of NO_(x) and much moreconcentrated in Co₂, making it easier to capture than with currenttechnologies.

Some suitable materials for application to SMFFs possess the formulasSr_(w)La_(x)Al_(y)(B)_(z)O_(2-α), where 0.01<w<1, 0.01<x<1, 0.01<y<1,0.01<z<1, 0<α<1 and B=Co, Fe, Cu (or a combination of the three).Basecoats applied to SMFFs were shown to be stable and crack free to700° C.

The general oxygen separation process involves the pressurization(between 25 and 75 psi) of the vessel containing the supported metaloxide with air at 200° C. The vessel is heated under pressure to 400° C.and then cooled back to 200° C. The pressure is released and excessnitrogen pulled off via moderate vacuum. High vacuum is then applied andthe vessel heated to 400° C. again, whereby the oxygen previouslyadsorbed will be desorbed and fed into a compressor for use in the givenindustrial process. One suitable design for an oxygen separation systemto carry out this process is illustrated in FIG. 12.

Example 9 Cyclic Catalytic Reformer for Hydrocarbon Fuels

A fixed bed cyclic redox (chemical looping) system utilizing a metaloxide oxygen carrier for partial oxidation of liquid fuel (jet fuel,diesel, kerosene, gasoline, etc) is described and illustratedschematically in FIG. 1A. The reformer consists of a small heated bed ofsulfur tolerant partial oxidation catalyst and operates by alternateexposure to air and vaporized fuel. Carbon deposition and steamrequirements and, possibly, the need for a prereformer are reduced oreliminated by this cyclic mode. This cyclic operation also eliminatesthe need for an expensive air separation unit or for H₂/N₂ separation.

A compact, lightweight reforming system for obtaining hydrogen foraviation fuel cell applications. The system is based on: 1) the partialoxidation of hydrocarbons by an oxygen carrier which can alternatelyadsorb oxygen and catalyze partial oxidation of fuel and 2) apost-processing module for hydrogen separation based on a hydrogentransport membrane.

Some suitable oxygen carrier materials include: 1)Ce_(1-x-y)M_(x)M′_(y)O_(2-*) (where M=cations of La, Sr, Ba, or othernon-reducible metals and MN=cations of Co, Ni, and Cu; and 0.01<x<0.99,0.01<y<0.99, and 1<δ<2.2) as well as the same transition metalsdeposited on a high surface area support such as alumina, magnesiumoxide, ceria, magnesium aluminate, aluminosilicates, or mesoporoussilica materials.

The addition of molybdenum to cobalt enhances sulfur tolerance,desulfurization activity, and will impart some cracking activity tocobalt. 2) Co, Ni, and Cu and Co—Mo supported on Al₂O₃, MgO, CeO₂, orMgAl₂O₄.

The supported base metal catalysts are prepared by incipient wetness. Atypical synthesis includes suspending 10 grams of support (Al₂O₃, MgO,CeO₂, or MgAl₂O₄) in an aqueous solution of the desired metal (Co)nitrate (and ammonium molybdate) without any supernatant liquid. Theslurry is dried by evaporation and then heated in an oven at 120° C. for8 hours. Following drying, the solid is calcined at 600° C. for 12-24hours in order to decompose the nitrate and provide a supported metaloxide product. If desired, the oxide may then be reduced to elementalmetal by flowing H₂ over the catalyst at 600° C. for 8 hours.

Example 10 Cyclic Catalytic Reforming of Hydrocarbon Fuels—Co-fed System

A process for the cyclic catalytic reforming of a hydrocarbon fuelutilizes a compact reformer system based on a cyclic (chemical looping)partial oxidation for generating syngas from liquid hydrocarbon logisticfuels (e.g., JP-8, JP-5, Jet-A, diesel, etc.). A reformer incorporatinga small heated bed of sulfur tolerant partial oxidation catalystalternately exposed to air and vaporized fuel is employed. This cyclicmode will potentially reduce the amount of carbon deposited and theamount of steam required. FIG. 13 schematically illustrates the processflow of the reforming operation in a co-fed air/pulsed fuel system usingcertain oxygen carrying catalysts.

In this process, air is passed continuously over the oxygen carrying (oroxygen storing) catalyst and pulses of fuel are delivered periodically,by co-feeding with the air flow, as shown schematically in FIG. 1C. Onesystem which may be suitably employed for carrying out the pulsed,co-fed reforming process is illustrated in FIG. 14. This technologydisplays the following characteristics: (1) Process operating conditionsare relatively mild: pressure of 1 atmosphere and temperature between550° C. and 750° C.; (2) H₂:CO ratio is continuously variable from <1to >5 (preferably between 0.9 and 2) by variation of temperature, spacevelocity, and feed composition (i.e., air/fuel ratio); (3) The processdoes not use steam. Carbon (coke) formation is dealt with by alternatingexposure to fuel rich and fuel lean conditions; (4) Thermal managementobtained by splitting reaction into temporally and/or spatiallyseparated carrier and fuel oxidation (carrier reduction) reactions; (5)Multiple beds enable continuous delivery of reformate; and (6) Fuelsulfur can be removed by hydrodesulfurization of organosulfides in thehydrogen rich product stream if the catalyst bed is made sufficientlylong.

The catalyst and similarly hot internal surfaces are successively andperiodically exposed to fuel and then to air. The resulting deposits canbe readily removed by exposure to air. Even on inert inorganic (e.g.,ceramic or glass) surfaces, coating internal surfaces with the oxygencarrier (catalyst) can impart carbon oxidation activity, which can, ofcourse, eliminate the problem of carbon deposition over time. Theprocesses responsible for carbon deposition also liberate hydrogen whichcan be separated down-stream. Even with the occurrence of carbonization,loss of efficiency is not inevitable in the cyclic PO_(x) process.

Some suitable catalyst (oxygen carriers) are selected from the genericcomposition Sr_(2-2x)La_(2x)B_(2-2y)Al_(2y)O_(*), where B=Co and/or Fe,0.1<x<0.8, 0.1<y<0.5, and 4<*<5.8. In some cases, molybdenum may beadded to the catalyst to enhance sulfur tolerance, desulfurizationactivity, and impart additional cracking activity to cobalt and/or iron.

Example 11 Cyclic Catalytic Reformer for Hydrocarbon Fuels—SequentialFeeds

This variation of a reforming process comprises the partial oxidation ofhydrocarbons by an oxygen carrier/catalyst which can alternately adsorboxygen and catalyze partial oxidation of fuel. The catalyst andsimilarly hot internal surfaces are successively and periodicallyexposed to fuel and then to air, in a manner like that illustrated inFIG. 1A. The resulting deposits on the catalyst can be readily removedby exposure to air. Even on inert inorganic (e.g., ceramic or glass)surfaces, coating internal surfaces with the oxygen carrier (catalyst)can impart carbon oxidation activity, which can, potentially eliminatethe problem of carbon deposition over time. The processes responsiblefor carbon deposition also liberate hydrogen which can be separateddown-stream. Even with the occurrence of carbonization, loss ofefficiency is not inevitable in the cyclic PO_(x) process.

Some suitable catalysts are selected from the generic compositionSr_(2-2x)La_(2x)B_(2-2y)Al_(2y)O_(δ), wherein B=Co and/or Fe, 0.1<x<0.8,0.1<y<0.5, and 4<δ<5.8. The addition of molybdenum to the catalyst mayenhance sulfur tolerance, desulfurization activity, and impartadditional cracking activity to cobalt and/or iron. These materialsprovide partial oxidation and hydrocarbon cracking activity via metaland acid sites, respectively. Formation of coke at this stage iseliminated by the oxidation activity of catalysts and the cyclic mode ofoperation. Embodiments of the catalysts also tolerate the presence ofsulfur in the fuel because cobalt forms a metal sulfide phase whichretains its oxidation activity.

Example 12 Coal Gasification Process

Exemplary metal oxide oxygen carriers/catalysts that are suitable forcoal gasification include Fe₃O₄, Co₃O₄, calcium carbonate, calciumoxide, FeTiO₃, Mn_(1-x)Fe_(x)O_(y), coal fly ash, and materialspossessing the general formula M_(1-x-y)A_(x)(B)_(y)O_(z), wherein M=Co,Fe, or Mn; A is Ce, Zr, or both; and B is a basic metal dopant such asLa or Ca. Catalysts are pelletized using binders such as aluminum oxide(and boehmite), titania, colloidal silica, and magnesium oxide. Selecteddoped ceria materials also displayed good activity. However, they aremore expensive than the other materials. An additional, albeitsurprising, observation is that the doped ceria materials investigateddisplayed much lower oxygen storage capacity than Fe₂O₃ or Fe₃O₄, e.g.,15× lower. These iron oxides provide a very exothermic heat ofregeneration, since the oxides are apparently reduced to the metal underoperating conditions. Subsequent oxidation of the catalyst, under thesecircumstances, provides a significant source of thermal energy forutilities or preheating of fluidizing gases.

Silica-bound coal fly ash proved to be the most durable of all boundmaterials investigated. Thus, in embodiments, fly ash is used as apotential catalyst or catalyst support.

A challenge in chemical looping technology using fluidized bed systemsis the fragility of catalyst pellets. Accordingly, in embodiments, theselected oxygen-carrying materials described herein have enhancedattrition resistance. In certain preferred embodiments, by combiningoxygen-carrying and support components into one composition, amechanically strong catalyst possessing activity for conversion of coalto synthesis gas is obtained.

Using a mixture of catalyst (Fe₃O₄), cornstarch, and binder(polyvinylbutyral) allows for strong, but still porous catalyst granulesto be prepared upon sintering. A 125 mL Nalgene bottle was charged with40 grams of catalyst powder, 24 grams cornstarch, and 4 grams polyvinylbutyral (PVB). To this mixture was added 10 hardened zirconia grindingmedia and enough acetone to fill the bottle. The mixture was then placedon a ball mill for 1 hour. After drying in an evaporating dish, withconstant stirring, the residue was allowed to dry in a fume hoodovernight. The resulting powder was then sieved to less than 45 mesh andpressed in a 2¼ inch die to 20,000 pounds (5,030 psi) for four minutes.The large pellet was sintered at 1025° C. for four hours, 1° C./minuteramp rate. Once tablets were formed as such, they were shattered,ground, and sieved to the desired mesh size (generally 20-40).

Another suitable coal gasification catalyst that serves as an oxygencarrier has the general formula Ce_(1-x)M_(x)O_(2-δ) wherein M=Fe, Mn,or Ni and 0.7<x<0.99. For example, Ce_(0.7)Mn_(0.3)O₂ andCe_(0.7)Ni_(0.3)O_(1.8). In embodiments, a ceramic carrier form (e.g.,fly ash or iron oxide beads) is impregnated with catalyst. This may beachieved by addition of the pellets to a solution of the desired metalions or metal complex species in the required concentrations. Excesssolvent may be removed by evaporation and the dry beads calcined at 200°C.-1000° C., depending on the catalyst deposited.

Pellets may be fabricated by tumbling powder as catalyst is sprayed ontothe pellets or by spray drying. Forms other than spheres may befabricated. In embodiments, cylindrically symmetric forms (such as bars,tubes, spaghetti, and miniliths) are fabricated using extrusion or (inthe case of ring or tubular forms) isostatic pressing. This involves thepreparation of a paste or dough of the relevant powder with organicbinders, dispersing agents, waxes, and other combustible additives (forporosity enhancement described above). An extruder incorporating a dieof the appropriate cross section is used for the extrusion operation.The extruded green bodies are sintered at temperatures of 1000-1700° C.,depending on the material being sintered. The extruded form may comprisecatalyst or of carrier material: the procedure to be employed may be thesame in the two cases. Application of the catalyst to support carriersmay be performed as described above for support beads.

A dual fluidized bed configuration (similar to fluidized catalyticcracking) or a switched feed single fluidized bed system may beemployed. However, several other embodiments, such as a switched feedmoving bed and entrained flow configurations are possible. Selection ofthe reactor type is typically based on engineering analysis of thepotential performance of each type as well as consideration of theiradvantages and disadvantages. One variation of the switched-feed singlebed system is an air fed-vibrating bed system. This allows for thereduction or elimination of a diluent gas feed on gasification. Thevibration may be applied during both carrier oxidation and gasification.Frequency, amplitude, and source of vibration are important variableswhose influence must be determined by experimentation. The vibrationalsource may be either vibrating baffles, an air activated piston, or anultrasonic horn, or any other type of suitable vibration source. Thisvibrationally fluidized system, as with any fluidized bed design, willrequire design of fluidized bed internals.

The design of fluidized bed internals, including baffles, heat exchangertubes, separators, and distributor plates, depends on the particularreactor configuration chosen, the particular process requirements, andthe predicted influence of component design on fluidized bed behavior.(FIG. 15)

The coal gasification process may be modified, if desired, by feedingother substances, such as biomass, waste, scrap tires, or otheropportunity fuels could be fed separately or concurrently with coal forgasification. Because a low operating temperature (≦900° C.) isemployed, the gasifier preferably operates in an ashing, rather thanslagging mode. In still other variations of the coal gasificationprocess, inorganic waste streams (e.g., ash) are processed for use asthe oxygen carrier.

Additional variations of the coal gasification process include 1)conversion of biomass to synthesis gas; 2) chemical looping partialoxidation of hydrocarbons; 3) chemical looping combustion of solid fuelsincluding coal, biomass, heavy reside, etc.; 4) chemical loopingcombustion of hydrocarbons; and 5) chemical looping hydrogen production.

Example 13 Catalysts and Process for Selective HydrocarbonDehydrogenation/Oxidative Coupling

Hydrocarbon dehydrogenation/oxidative coupling chemistry proceeds at thesurface of metal oxide catalysts possessing the general formulaAB_(1-x)B′_(x)O_(y) (A=Sr or Ba; B=Ce or Zr; and B′=Y or Yb; and0<x<0.5)/MO_(x) (where M=Ce, Mn, or Ni) or x % MO_(x)/y % A₂WO₄/MgO (orSiO₂), where A=Na or K, 1<x<3, and 3<y<8; and M=Ce, Mn, or Ni. Catalystsfor promoting the selective and spontaneous oxidative dehydrogenation orcoupling of hydrocarbons, is based on the application of super-base,amphoteric (i.e., containing both acid or electrophilic, and base sites)catalysts. Catalysis is based on a mixture of both oxygen storage andoxidative dehydrogenation catalyst components in contact with oneanother.

The synergistic role of the catalyst components and their functions isonly fully exploited when optimum process operating conditions are alsoemployed. Among the potential advantages of embodiments of thistechnology are (1) Molecular oxygen is not present as with a co-feedconfiguration. This reduces the occurrence of destructive side reactionsand enhances selectivity towards desired non-CO_(x) products; (2)Chemical looping oxidative dehydrogenation is exothermic, in contrast tothermal dehydrogenation, which is endothermic. Hence, considerableenergy savings may result; (3) Cryogenic oxygen separation from theatmosphere is eliminated since oxygen for promoting the subject reactionis separated directly from air via the chemical looping system; (4)Natural gas is a plentiful and inexpensive chemical feedstock forethylene synthesis thereby contributing to low ethylene feedstock costs.In addition, the presence of ethane and other light hydrocarbons innatural gas participate in enhanced ethylene production.

The catalysis strategy for promoting the oxidative dehydrogenationreaction relies on either basic or amphoteric sites for activating C—Hbonds. Additionally, an oxygen storage function must be present to allowfor chemical looping. Of the proposed oxidative dehydrogenationcomponents, the first category, the super-bases of general formulaAB_(1-x)B′_(x)O_(y), are represented most effectively byBaZr_(1-x)Y_(x)O_(2.5-δ) and are the currently preferred catalystmaterials. In the case of the amphoteric catalysts, the transition metaloxide serves as an oxygen storage component. These species are expectedto exhibit a somewhat unique mechanism of reactivity relative tostrongly basic species. In the case of the MTM and MTS systems, thelikely C—H activation site is a surface W═O which is expected to be moreacidic than basic due to the high electrophilicity of the W(VI) ion.Manganese oxide, as indicated above, is included in some embodiments inorder to provide oxygen storage capacity.

Use of these materials in chemical looping ODH is implemented by: 1)preparing catalysts possessing the compositionAB_(1-x)B′_(x)O_(y)/MO_(x) (A=Sr or Ba; B=Ce or Zr; B′=Y or Yb; 0<x<0.5;M=Ce, Mn, or Ni); and x % MO_(x)/y % A₂WO₄/MgO (or SiO₂), where A=Na orK, 1<x<3, 3<y<8; and M=Ce, Mn, or Ni; 2) preparing granules of materialof the above discussed compositions for promoting the overall subjectreaction; 3) incorporating the most active catalysts into a fixed bedreactor and determining their performance towards efficiently andselectively promoting alkane oxidative dehydrogenation in representativegas mixtures; and 4) optimizing catalyst materials and processconditions.

The materials are employed in a cyclic (chemical looping) process basedon a circulating fluidized bed process and system (FIG. 16) or aswitched (between air and fuel) feed fluidized bed system or switchedfeed fixed bed system, in which air and fuel feeds are alternated.

Example 14 Catalysts and Process for Direct Generation of HydrogenPeroxide

Nanostructured catalyst materials prepared by “nanocasting”carbon/nitrogen-containing metal complexes in the pores of mesoporoussilicas or by self-assembling such complexes with inorganic (e.g.,silica) precursors and their application in a process for the directgeneration of hydrogen peroxide is discussed in this example. Inembodiments, new catalysts are based on the thermal decomposition ofspecific metal complexes (Pt, Pd, Au, Ag, Co, Ni, Cu, or Ruphthalocyanine or tetraphenylporphine) in the pores of mesoporous silicamaterials or by the spontaneous self-assembly of metal complex andinorganic framework precursors. The anticipated net effect of thesemetallomacrocycle-based nanostructured catalysts will be 1) to providehighly (even atomically) dispersed active catalyst sites, 2) to providehigh surface area and pore volume, and 3) to provide specific benefitsof other properties of the nanostructured materials. Thesemultifunctional catalyst materials are used in a chemical loopingprocess for catalyzing the direct reaction of hydrogen and oxygen toform hydrogen peroxide. The cyclic process design allows: (1) Separationof oxygen from air, (2) use of undiluted hydrogen with minimal explosionhazard because hydrogen and oxygen are spatially separated when eachcontacts the catalyst and/or 3) elimination of organic solvent use.

In the chemical looping process in which oxygen or hydrogen isincorporated into a component of the catalyst in one zone of theprocess, followed by transport of the “charged” catalyst to the oppositezone, where it reacts with oxygen or hydrogen to form H₂O₂ and theproduct and catalyst are separated by motion of the catalyst in thereactor. Chemical looping can be better understood by consideration ofthe reaction scheme for this process:

M+O₂

Ox  (1)

Ox+H₂

Re  (2)

Re+O₂

H₂O₂  (3)

Overall: H₂+O₂

H₂O₂  (4)

where Ox and Re refer to the oxidized and reduced forms of the catalyst,respectively. In a sense, this is quite similar to a variety of chemicalprocesses, including the anthraquinone, Wacker, and other processes inwhich a redox intermediate is employed. Embodiments of this processoffer various potential advantages, including: 1) the ability toseparate O₂ from air, 2) the ability to use higher concentrations andpressures of hydrogen and oxygen, 3) enhanced safety obtained byseparation of hydrogen and oxygen, and 4) the benefits of a fluidizedbed.

Example 15 Catalytic Cyclic Process for Waste Gasification

A cyclic process in which an oxygen carrier is alternately oxidized inair and reduced by contact with waste species (waste feed, char,volatiles, etc.), resulting in gasification of the waste and subsequentcarrier regeneration potentially exhibits excellent heat transfercharacteristics, relatively low operating temperature, and minimal taraccumulation. The process makes use of the redox properties of selectedmetal oxide materials and their separate interactions with air and wastematerial. This process for waste gasification involves the combinationof two technologies: chemical looping separation of oxygen from air andfluidized bed gasification catalyzed by the oxygen carriers.

Embodiments of this technology will offer the following potentialattributes: 1) feed flexibility brought about by pre-pyrolysis of wasteinto char and volatiles; 2) lower cost for air separation; 3) a gasifierthat is optimal for conversion of waste feed with minimal heat loss andslag or ash processing without accumulation of tar in cooler downstreamparts of the system; 4) the excellent heat transfer characteristics offluidized bed gasifiers; 5) reduced tar accumulation owing to presenceof oxidized oxygen carrier in vulnerable regions of the gasifier; and 6)improved syngas cleanup.

The technology makes use of fluidized beds for several purposes: (1)“Charging” of oxygen carriers (i.e., saturation with oxygen); (2)Reaction with solid waste, char, and volatiles with reduced taraccumulation; (3) Clean-up of synthesis gas using sorptive additives.Ultimately, in the overall concept, waste gasification may be conductedusing a chemical looping reactor to effect combined air separation,waste gasification, and gross sulfur removal.

A system comprised of: (1) a preprocessing stage in which waste iscompacted and dried. The preprocessing stage consists of a retort fordrying and waste heating, along with a condenser for collection of tarand oils. (2) An ASU/gasification reactor based on Eltron's chemicallooping technology. In embodiments, the preprocessed waste stream isdevolatilized (using waste heat from the gasifier and syngas quenchcooling) by pyrolysis upon its entrance into the gasifier chamber. Thus,it is possible that pyrolysis and gasification can be combined in thechemical looping gasifier reactor. 3) A syngas quench cooler. 4) A warmgas cleanup module. This may consist of a third fluidized bed or of adownstream sorption module. Warm gas clean-up would be performed eitherby the use of sorbents in a third fluidized bed or of downstreamadsorbent beds containing materials selected from zinc oxide, zinc oxidesupported copper (low temperature water gas shift catalyst), or theregenerable sorbents zinc ferrite or zinc titanate. 5) A hydrogenseparation module.

The metal oxide catalysts are selected from Fe₃O₄, Co₃O₄, Mn₁ _(—)_(x)Fe_(x)O_(y), and materials possessing the general formulaM_(1-x-y)A_(x)(B)_(y)O_(z), (where M=Co, Fe, or Mn; A is Ce, Zr, or acombination of the two; and B is a basic metal dopant such as La or Ca).Other compositions may be investigated as deemed necessary. Thecatalysts may be pelletized using one of the following binders: yttriumstabilized zirconium (YSZ), aluminum oxide, boehmite, gibbsite, andmagnesium oxide.

Example 16 Partial Oxidation of Crude Glycerol to Produce Synthesis Gas

A new process of partially oxidizing glycerol (FIG. 17), calledCycloForming™ potentially produces high levels of syngas and anexcellent distribution of H₂ and CO for Fischer-Tropsch Synthesis at lowtemperatures in contrast to other processes such as pyrolysis whichproduce mainly liquid. In a representative study, 0.5 g ofSr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O_(5.3) granules were packed into afixed bed reactor and heated to 700° C. Catalyst oxidation comprises oneleg of the chemical looping cycle. This was performed in situ by feedingair over the catalyst bed for 1-30 minutes prior to introducingglycerol. The catalyst bed was then purged with helium and the atomizedglycerol was introduced at a flow rate of 0.27 g/min. A sample of theproduct gas was taken and analyzed using a gas chromatograph at a settime from when the gaseous products began to be produced. Several cyclesalternating between air and glycerol were performed with variableglycerol exposure times.

Representative catalysts have shown excellent resistance to catalystfouling from the residual KOH in crude glycerol (residualtransesterification catalyst). Besides increasing the efficiency of thereforming reaction, the KOH imparts reverse water-gas-shift capacity tothe catalyst, which converts the H₂O stream to H₂ (see FIG. 18). Forthis experiment porous catalyst granules of yttria-stabilized zirconia(YSZ) were prepared and coated with 6.6 wt %Sr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O_(5.3). 20 g of coated granules werepacked into a fixed bed reactor and heated to 800° C. Catalyst oxidationcomprises one leg of the chemical looping cycle. This was performed insitu by feeding air over the catalyst bed for 1-30 minutes prior tointroducing glycerol. The catalyst bed was then purged with helium andthe atomized glycerol, glycerol with water, or glycerol with water andKOH (simulated crude glycerol) was introduced with the flow rate variedfrom cycle to cycle. For this experiment, the glycerol cycle length waslong (more than 1 hour) to allow for equilibration of the reaction ateach flow setting. Samples of the product gas were taken and analyzedusing a gas chromatograph. Several cycles were performed over a 23 dayperiod. For the last 6 days, KOH stability was tested. The simulatedcrude glycerol was introduced into the reactor at 0.23 g/min for about 8hours per day and the catalyst was reoxidized with air overnight. FIG.19 shows that even with KOH in the crude glycerol, the catalyst isstable for more than 40 hours of exposure. Similar catalysts having thegeneral formula Sr_(v)La_(w)B_(x)B′_(y)B″_(z)O_(δ), wherein B=Co or Fe;B′=Al or Ga; B″=Cu; 0.01<v<1.4; 0.1<w<1.6; 0.1<x<1.9; 0.1<y<0.9;0<z<2.2; and 3<δ<5.5 are expected to have similar resistance to catalystfouling from crude glycerol, and will be similarly active for catalyzingthe partial oxidation of glycerol to produce synthesis gas.

Without further elaboration, it is believed that one skilled in the artcan, using the description herein, utilize the present invention to itsfullest extent. The foregoing embodiments are to be construed asillustrative, and not as constraining the remainder of the disclosure inany way whatsoever. While the preferred embodiments of the inventionhave been shown and described, modifications thereof can be made by oneskilled in the art without departing from the spirit and teachings ofthe invention. The embodiments described herein are exemplary only, andare not intended to be limiting. Many variations and modifications ofthe invention disclosed herein are possible and are within the scope ofthe invention. Accordingly, the scope of protection is not limited bythe description set out above, but is only limited by the claims whichfollow, that scope including all equivalents of the subject matter ofthe claims. In the following discussion and in the claims, the terms“including” and “comprising” are used in an open-ended fashion, and thusshould be interpreted to mean “including, but not limited to . . . ”.Each original claim is incorporated into the specification as anembodiment of the invention. Thus the original claims are a furtherdescription and are an addition to the preferred embodiments. Thedisclosures of all patents, patent applications and publications citedherein are hereby incorporated herein by reference, to the extent thatthey provide exemplary, procedural or other details supplementary tothose set forth herein.

REFERENCES

The following references are cited in the foregoing text, or may behelpful as additional background information.

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1. A process comprising: alternately contacting an oxygen-carryingcatalyst with a reducing substance, or a lower partial pressure of anoxidizing gas, and then with said oxidizing gas or a higher partialpressure of said oxidizing gas, whereby the catalyst is alternatelyreduced and then regenerated to an oxygenated state, wherein saidoxygen-carrying catalyst comprises at least one metal oxide-containingmaterial selected from the group consisting of: (a) compounds having theformula Ce_(x)B_(y)B′_(z)B″O_(δ), wherein B=Ba, Sr, Ca, or Zr; B′=Mn,Co, or Fe; B″=Cu; 0.01<x<0.99; 0<y<0.6; 0<z<0.5; and 1<δ<2.2; (b)compounds having the formula Sr_(v)La_(w)B_(x)B′_(y)B″_(z)O_(δ), whereinB=Co or Fe; B′=Al or Ga; B″=Cu; 0.01<v<1.4; 0.1<w<1.6; 0.1<x<1.9;0.1<y<0.9; 0<z<2.2; and 3<δ<5.5; (c) Ce_(1-x-y)Ni_(x)B_(y)O_(2-*),wherein B=Zr, Ba, Ca, La, or K; 0.02<x<0.1; 0<y<0.1; and 0.02<*<0.15;(d) M_(1-x-y)A_(x)(B)_(y)O_(z), wherein M=Co, Fe, or Mn; A=Ce, Zr, orboth; B=La or Ca; 0.01<x<0.99; 0.01<y<0.99; 2<z<3.5; and (x+y)≦1; (e)AB_(1-x)B′_(x)O_(y), wherein A=Sr or Ba, B=Ce or Zr, B′=Y or Yb, and0<x<0.5, on a support comprising MO_(x), wherein M=Ce, Mn, or Ni, or ona support comprising x % MO_(x)/y % A₂WO₄/(MgO or SiO₂), wherein M=Ce,Mn, or Ni, and A<Na or K, 1<x<3, and 3<y<8; (f) unary metal oxidesselected from the group consisting of Fe₂O₃, Fe₃O₄, MnO_(x), CoO_(x),NiO_(x), wherein 1<x<2, CaCo₃, Ca(OH)₂; (g) binary metal oxides selectedfrom the group consisting of FeTiO₃, Mn_(1-x)CuO₂, andMn_(1-x)Fe_(x)O_(y), wherein 0.01<x<0.99, 1<y<1.5; and (h) coal asheither as a catalyst material itself or as a support for said unary orbinary metal oxides, wherein said reducing substance, when contactedwith said oxygen-carrying catalyst, is converted to at least onechemical product.
 2. The process of claim 1, wherein said reducingsubstance is selected from the group consisting of gas, liquid, andsolid substances.
 3. The process of claim 1, wherein said contactingcomprises: alternately exposing a fixed bed containing said catalyst tosaid reducing substance and to said oxidizing gas, or exposing saidfixed bed containing said catalyst to a continuous feed of saidoxidizing gas and intermittently feeding said reducing substance.
 4. Theprocess of claim 1, wherein said contacting comprises: circulating saidcatalyst in a fluidized bed system during said alternate contacting ofsaid oxygen-carrying catalyst with a reducing substance, or a lowerpartial pressure of an oxidizing gas, and then with said oxidizing gasor a higher partial pressure of said oxidizing gas.
 5. The process ofclaim 1, wherein said contacting comprises: circulating said catalyst ina fluidized bed system wherein said catalyst is reduced in a reactor andis circulated to a regeneration unit for contacting with said oxidizinggas or higher partial pressure of said oxidizing gas.
 6. The process ofclaim 1, wherein said reducing substance comprises a gaseoushydrocarbon, said chemical product is synthesis gas, and said catalystis active for catalyzing the partial oxidation of said hydrocarbon,wherein said catalyst comprises: Ce_(x)B_(y)B′_(z)B′_(w)O_(δ), whereinB=Ba, Sr, Ca, or Zr; B′=Mn, Co, or Fe; B′=Cu; 0.01<x<0.99, 0<y<0.6,0<w<0.5, and 1<δ<2.2, or Ce_(1-x-y)Ni_(x)B_(y)O_(2-*), wherein B=Zr, Ba,Ca, La, or K; 0.02<x<0.1; 0<y<0.1; and 0.02<*<0.15, orSr_(v)La_(w)B_(x)B′_(y)B_(z)″O_(δ), wherein B=Co or Fe; B′=Al or Ga;B″=Cu, 0.01<v<1.4; 0.1<w<0.6; 0.1<x<1.9; 0.1<y<0.9; 0<z<2.2; and3<δ<5.5; or M_(1-x-y)A_(x)(B)_(y)O_(z), wherein M=Co, Fe, or Mn; A=Ce,Zr, or both; B=La or Ca; 0.01<x<0.99; 0.01<y<0.99; 2<z<3.5; and x+y≦1.7. The process of claim 6, wherein said catalyst comprisesCe_(0.95)Ni_(0.05)O_(1.95), Ce_(0.98)Ni_(0.02)O_(1.98), orCe_(0.90)Ni_(0.05)Ba_(0.05)O_(1.95).
 8. The process of claim 1, whereinsaid reducing substance comprises a liquid hydrocarbon fuel, saidproduct comprises synthesis gas, and said catalyst is active forcatalyzing the partial oxidation of said liquid hydrocarbon fuel,wherein said catalyst comprises Sr_(v)La_(w)B_(x)B′_(y)B″_(z)O_(δ),wherein B=Co or Fe, B′=Al or Ga, B″=Cu, 0.01<v<1.4, 0.1<w<1.6,0.1<x<1.9, 0.1<y<0.9, 0<z<2.2, and 3<δ<5.5.
 9. The process of claim 8,wherein said oxygen-carrying catalyst comprisesSr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O₅,Sr_(0.31)La_(1.43)Co_(1.33)Al_(0.24)O_(4.81),Sr_(0.3)La_(1.27)Co_(1.74)Al_(0.21)O_(5.13), orSr_(0.02)La_(0.26)Fe_(1.63)Al_(0.02)Cu_(2.08)O_(4.97).
 10. The processof claim 1, wherein said reducing substance comprises liquid hydrocarbonfuel and lower partial pressure oxidizing gas in combination, saidproduct comprises synthesis gas, said catalyst is active for catalyzingthe partial oxidation of said liquid hydrocarbon fuel, and said processcomprises co-feeding both said fuel and a lower partial pressure of anoxidizing gas to said catalyst in a reforming reactor, to reduce saidcatalyst, and produce synthesis gas, and exposing said reduced catalystto said higher partial pressure of said oxidizing gas in the absence ofsaid fuel to regenerate said catalyst.
 11. The process of claim 10,further comprising separating H₂ from said synthesis gas.
 12. Theprocess of claim 10, wherein said contacting comprises contacting saidcatalyst at a temperature less than or equal to 900° C.
 13. The processof claim 10, wherein said catalyst comprisesSr_(v)La_(w)B_(x)B′_(y)B″_(z)O_(δ), wherein B=Co or Fe, B′=Al or Ga,B″=Cu, 0.01<v<1.4, 0.1<w<1.6, 0.1<x<1.9, 0.1<y<0.9, 0<z<2.2, and3<δ<5.5.
 14. The process of claim 13, wherein said catalyst comprisesSr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O₅,Sr_(0.31)La_(1.43)Co_(1.33)Al_(0.24)O_(4.81),Sr_(0.3)La_(1.27)Co_(1.74)Al_(0.21)O_(5.13), orSr_(0.02)La_(0.26)Fe_(1.63)Al_(0.02)Cu_(2.08)O_(4.97).
 15. The processof claim 1, wherein said reducing substance comprises a liquid fuelselected from the group consisting of diesel, gasoline, jet fuel,alcohols, glycerol, and plant oils.
 16. The process of claim 1, whereinsaid reducing substance comprises coal particles, said product comprisessynthesis gas, and said catalyst is active for catalyzing thegasification of said coal particles, wherein said catalyst comprises atleast one metal oxide-containing material selected from the groupconsisting of Fe₂O₃, Fe₃O₄, MnO_(x), CoO_(x), NiO_(x), FeTiO₃, CaCo₃,CaO, and Mn_(1-x)Cu_(x)O_(y) or Mn_(1-x)Fe_(x)O_(y) wherein 0.01<x<0.99and 1<y<1.5, and coal ash either as a catalyst material itself or as asupport for said metal oxide-containing material.
 17. The process ofclaim 1, wherein said reducing substance comprises biomass particles,said product comprises synthesis gas, and said catalyst is active forcatalyzing the gasification of said biomass particles, wherein saidcatalyst comprises at least one metal oxide-containing material selectedfrom the group consisting of Fe₂O₃, Fe₃O₄, MnO_(x), CoO_(x), NiO_(x),FeTiO₃, CaCo₃, CaO, and Mn_(1-x)Cu_(x)O_(y) or Mn_(1-x)Fe_(x)O_(y)wherein 0.01<x<0.99 and 1<y<1.5, and coal ash either as a catalystmaterial itself or as a support for said metal oxide-containingmaterial.
 18. The process of claim 1, wherein said reducing substancecomprises a hydrocarbon, said product comprises a dehydrogenatedhydrocarbon, and said catalyst is active for oxidatively dehydrogenatingsaid hydrocarbon, wherein said catalyst comprises:Ce_(x)B_(y)B′_(z)B″_(w)O_(δ), wherein B=Ba, Sr, Ca, or Zr; B′=Mn, Co, orFe; B″=Cu; 0.01<x<0.99, 0<y<0.6, 0<z>0.5, 0<w≦0.5, and 1<δ<2.2, orSr_(v)La_(w)B_(x)B′_(y)B″_(z)O_(δ), wherein B=Co or Fe, B′=Al or Ga,B″=Cu, 0.01≦v≦1.4, 0.1<w<1.6, 0.1<x<1.9, 0.1<y<0.9, 0<z<2.2, and3<δ<5.5, or AB_(1-x)B′_(x)O_(y), wherein A=Sr or Ba, B=Ce or Zr, B′=Y orYb, and 0<x<0.5, on a support comprising MO_(x), wherein M=Ce, Mn, orNi, or on a support comprising x % MO_(x)/y % A₂WO₄/(MgO or SiO₂),wherein M=Ce, Mn, or Ni, and A=Na or K, 1<x<3, and 3<y<8.
 19. Theprocess of claim 18, wherein said catalyst comprisesSr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O₅,Sr_(0.31)La_(1.43)Co_(1.33)Al_(0.24)O_(4.81), orSr_(0.3)La_(1.27)Co_(1.74)Al_(0.21)O_(5.13).
 20. The process of claim 1,wherein said reducing substance comprises a hydrocarbon, said productcomprises an oxidatively functionalized hydrocarbon, and said catalystis active for catalyzing the selective oxidation of said hydrocarbon bywhich at least one oxygenous function is inserted into said hydrocarbon,wherein said catalyst comprises: Ce_(x)B_(y)B′_(z)B″_(w)O_(δ), whereinB=Ba, Sr, Ca, or Zr; B′=Mn, Co, or Fe; B″=Cu; and 0.01<x<0.99, 0<y<0.6,0<w<0.5, and 1<δ<2.2), or Sr_(v)La_(w)B_(x)B′_(y)B″_(z)O_(δ), whereinB=Co or Fe, B′=Al or Ga, B″=Cu, 0.01<v<1.4, 0.1<w<1.6, 0.1<x<1.9,0.1<y<0.9, 0<z<2.2, and 3<δ<5.5).
 21. The process of claim 20, whereinsaid catalyst comprises Sr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O₅,Sr_(0.31)La_(1.43)Co_(1.33)Al_(0.24)O_(4.81) orSr_(0.3)La_(1.27)Co_(1.74)Al_(0.21)O_(5.13).
 22. A process forseparating oxygen from air, comprising: cyclically adsorbing anddesorbing oxygen on an oxygen-carrying catalyst comprisingCe_(x)B_(y)B′_(z)B″_(w)O_(δ), wherein B=Ba, Sr, Ca, or Zr; B′=Mn, Co, orFe; B′=Cu; and 0.01<x<0.99, 0<y<0.6, 0<w<0.5, and 1<δ<2.2), orSr_(v)La_(w)B_(x)B′_(y)B″_(z)O_(δ) (where B=Co or Fe, B′=Al or Ga,B′=Cu, 0.01<v<1.4, 0.1<w<1.6, 0.1<x<1.9, 0.1<y<0.9, 0<z<2.2, and3<δ<5.5, or Sr_(w)La_(x)Al_(y)(B)_(z)O_(2-α), wherein B=Co, Fe, Cu or acombination of any of those, 0.01<w<1, 0.01<x<1, 0.01<y<1, 0.01<z≦1, and0<α<1.
 23. The process of claim 22, wherein said adsorbing comprisesexposing said catalyst to pressurized air, and said desorbing comprisesexposing said catalyst to a vacuum when said catalyst contains adsorbedoxygen.
 24. The process of claim 22, wherein said catalyst is selectedfrom the group consisting of: Sr_(1.4)La_(0.6)Co_(1.6)Al_(0.4)O₅,Sr_(0.3)La_(1.27)Co_(1.74)Al_(0.21)O_(5.13),Sr_(0.31)La_(1.43)Co_(1.33)Al_(0.24)O_(4.81),Sr_(0.02)La_(0.26)Fe_(1.63)Al_(0.02)Cu_(2.08)O_(4.97),Ce_(0.5)Fe_(0.1)Cu_(0.4)O₂, CeCo_(0.5)Cu_(0.5)O₃,Ce_(0.12)Mn_(0.34)Co_(0.54)O_(1.64), andCe_(0.45)Zr_(0.05)Mn_(0.45)Cu_(0.05)O_(1.7).
 25. The process of claim 1,wherein said catalyst is supported on a sintered metal fiber filter. 26.The process of claim 1 wherein said reducing substance comprises acombustible waste material, said product is char and volatiles, and saidcatalyst comprises a metal oxide that is active for pyrolyzing saidwaste product.
 27. A process for the cyclic catalytic partial oxidationof a carbon-containing feedstock, comprising: (a) in an oxidation stage,passing air over a catalyst comprising a metal or metal oxide that iscapable of capturing oxygen from said air, to produce an oxidizedcatalyst and producing an effluent comprising oxygen-reduced air; (b) ina reduction stage, passing said feedstock over said oxidized catalyst tocreate a product gas comprising carbon monoxide and hydrogen, whereinsaid oxidized catalyst becomes reduced or partially reduced creating ametal or metal oxide; and (c) repeating (a) to reoxidize the catalyst,wherein said catalyst comprises at least one metal oxide selected fromthe group consisting of: Ce_(x)B_(y)B′_(z)B″O_(δ), wherein B=Ba, Sr, Ca,or Zr; B′=Mn, Co, or Fe; B″=Cu; 0.01<x<0.99; 0<y<0.6; 0<z<0.5; 1<δ2.2;Ce_(1-x-y)Ni_(x)B_(y)O_(2-*), wherein B=Zr, Ba, Ca, La, or K;0.02<x<0.1; 0.01<y<0.1; and 0.02<*<0.15, andSr_(v)La_(w)B_(x)B′_(y)B″_(z)O_(δ), wherein B=Co or Fe; B′=Al or Ga;B″=Cu; 0.01<v<1.4; 0.1<w<1.6; 0.1<x<1.9; 0.1<y<0.9; 0<z<2.2; and3<δ<5.5.
 28. The process of claim 27, wherein said feedstock comprisesglycerol.
 29. A process for the direct generation of hydrogen peroxide,comprising: (a) in an oxidation stage, passing air over a catalystcomprising a metal or metal oxide that is capable of capturing oxygenfrom said air, to produce an oxidized catalyst and producing an effluentcomprising oxygen-depleted air; (b) passing hydrogen over said oxidizedcatalyst in a reduction stage to create a product gas comprisinghydrogen peroxide, wherein said oxidized catalyst becomes reduced orpartially reduced; and (c) repeating (a) to reoxidize the catalyst,wherein said catalyst comprises a nanostructured catalyst comprising acarbon- or nitrogen-containing metal complex deposited in the pores of amesoporous support material, wherein said metal is selected from thegroup consisting of Pt, Pd, Au, Ag, Co, Ni, Cu or Ru.
 30. A process forcyclic reduction of carbon dioxide, comprising (a) in an oxidationstage, passing carbon dioxide over a catalyst comprising a metal ormetal oxide that is capable of capturing oxygen from said carbondioxide, to produce an oxidized catalyst and producing an effluentcomprising carbon monoxide; (b) in a reduction stage, passing hydrogenover said oxidized catalyst to produce water, whereby said oxidizedcatalyst becomes reduced or partially reduced; and (c) repeating (a) toreoxidize the catalyst, wherein said catalyst comprises iron.
 31. Theprocess of claim 30, further comprising recovering said water and carbonmonoxide.